Junfeng Ding

Growing Crystalline Chalcogenidoarsenates in Surfactants: From Zero-Dimensional Cluster to Three-Dimensional Framework

Although surfactants have been widely used to tailor the size, shape, and surface properties of nanocrystals and control the pore size and phases of mesoporous frameworks, the use of surfactants as reaction media to grow chalcogenide crystals is unprecedented. In addition, compared with ionic liquids, surfactants are much cheaper and can have multifunctional properties such as acidic, basic, neutral, cationic, anionic, or even block. These features suggest that surfactants could be promising reaction platforms for the development of novel chalcogenide crystals. In this work, we used chalcogenidoarsenates as a model system to demonstrate our strategy. By using three different surfactants as reaction media, we obtained a series of novel thioarsenates ranging from a zero-dimensional (0D) cluster to a three-dimensional (3D) framework, namely, [NH(4)](8)[Mn(2)As(4)S(16)] (1), [Mn(NH(3))(6)][Mn(2)As(2)S(8)(N(2)H(4))(2)] (2), [enH][Cu(3)As(2)S(5)] (3), and [NH(4)][MnAs(3)S(6)] (4). The band gaps (estimated from the steep absorption edges) were found to be 2.31 eV for 1 (0D), 2.46 eV for 2 (1D), 1.91 eV for 3 (2D), and 2.08 eV for 4 (3D). The magnetic study of 4 indicated weak antiferromagnetic behavior. Our strategy of growing crystalline materials in surfactants could offer exciting opportunities for preparing novel crystalline materials with diverse structures and interesting properties.

Surfactant media to grow new crystalline cobalt 1,3,5-benzenetricarboxylate metal-organic frameworks.

In this report, three new metal-organic frameworks (MOFs), [Co3(μ3-OH)(HBTC)(BTC)2Co(HBTC)]·(HTEA)3·H2O (NTU-Z30), [Co(BTC)]·HTEA·H2O (NTU-Z31), [Co3(BTC)4]·(HTEA)4 (NTU-Z32), where H3BTC = 1,3,5-benzenetricarboxylic acid, TEA = triethylamine, and NTU = Nanyang Technological University, have been successfully synthesized under surfactant media and have been carefully characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analysis, and IR spectromtry. NTU-Z30 has an unusual trimeric [Co3(μ3-OH)(COO)7] secondary building unit (SBU), which is different from the well-known trimeric [Co3O(COO)6] SBU. The topology studies indicate that NTU-Z30 and NTU-Z32 possess two new topologies, 3,3,6,7-c net and 2,8-c net, respectively, while NTU-Z31 has a known topology rtl type (3,6-c net). Magnetic analyses show that all three materials have weak antiferromagnetic behavior. Furthermore, NTU-Z30 has been selected as the heterogeneous catalyst for the aerobic epoxidation of alkene, and our results show that this material exhibits excellent catalytic activity as well as good stability. Our success in growing new crystalline cobalt 1,3,5-benzenetricarboxylate MOFs under surfactant media could pave a new road to preparing new diverse crystalline inorganic materials through a surfactant-thermal method.

Surfactant-thermal syntheses, structures, and magnetic properties of Mn-Ge-sulfides/selenides.

Although either surfactants or amines have been investigated to direct the crystal growth of metal chalcogenides, the synergic effect of organic amines and surfactants to control the crystal growth has not been explored. In this report, several organic bases (hydrazine monohydrate, ethylenediamine (en), 1,2-propanediamine (1,2-dap), and 1,3-propanediamine (1,3-dap)) have been employed as structure-directing agents (SDAs) to prepare four novel chalcogenides (Mn3Ge2S7(NH3)4 (1), [Mn(en)2(H2O)][Mn(en)2MnGe3Se9] (2), (1,2-dapH)2{[Mn(1,2-dap)2]Ge2Se7} (3), and (1,3-dapH)(puH)MnGeSe4(4) (pu = propyleneurea) under surfactant media (PEG-400). These as-prepared new crystalline materials provide diverse metal coordination geometries, including MnS3N tetrahedra, MnGe2Se7 trimer, and MnGe3Se10 T2 cluster. Compounds 1-3 have been fully characterized by single-crystal X-ray diffraction (XRD), powder XRD, UV-vis spectra, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Moreover, magnetic measurements for compound 1 showed an obvious antiferromagnetic transition at ~9 K. Our research not only enriches the structural chemistry of the transitional-metal/14/16 chalcogenides but also allows us to better understand the synergic effect of organic amines and surfactants on the crystallization of metal chalcogenides.

Anomalous exchange bias at collinear/noncollinear spin interface

We report on the interfacial magnetic coupling in manganite bilayers of collinear ferromagnetic La0.7Sr0.3MnO3 and noncollinear multiferroic TbMnO3. Exchange bias is observed at the Néel temperature of TbMnO3 (~41 K) due to the onset of long-range antiferromagnetic ordering in the Mn spin sublattice. Interestingly, an anomalous plateau of exchange bias emerges at the ordering temperature of Tb spins (~10 K), and we ascribe this unique feature to the strong coupling between Tb and Mn spin sublattices in TbMnO3, which in turn influences the magnetic coupling across the interface. On the other hand, the enhancement of coercivity in La0.7Sr0.3MnO3/TbMnO3 shows monotonous temperature dependence. Our results illustrate a strong interfacial magnetic interaction at the La0.7Sr0.3MnO3/TbMnO3 interface, highlighting the roles of competing spin orders, magnetic frustration, and coupling between multiple spin sublattices in artificial collinear/noncollinear spin heterostructures.

Exchange coupling and coercivity enhancement in cuprate/manganite bilayers

We report on the magnetic properties of cuprate/manganite bilayers composed of antiferromagnetic (AFM) La2CuO4 and ferromagnetic La0.70Sr0.30MnO3. The temperature dependent magnetization data indicate an interfacial spin-glass state. Furthermore, the bilayer exhibits significant enhancement of coercivity compared to the La0.70Sr0.30MnO3 single layer and reaches 705 Oe at 5 K. The dependence of coercivity on the AFM layer thickness indicates that the enhancement cannot be explained by the interfacial charge diffusion. Our results suggest that the exchange coupling between Mn and Cu spins and the magnetic frustration at the La2CuO4/La0.70Sr0.30MnO3 interface must be considered to harness the properties of cuprate/manganite heterostructures.

Interfacial magnetic coupling in ultrathin all-manganite La0.7Sr0.3MnO3-TbMnO3 superlattices

We report the growth and magnetic properties of all-manganite superlattices composed of ultrathin double-exchange ferromagnetic La0.7Sr0.3MnO3 and noncollinear multiferroic TbMnO3 layers. Spontaneous magnetization and hysteresis loops are observed in such superlattices with individual La0.7Sr0.3MnO3 layers as thin as two unit cells, which are accompanied by pronounced exchange bias and enhanced coercivity. Our results indicate substantial interfacial magnetic coupling between spin sublattices in such superlattices, providing a powerful approach towards tailoring the properties of artificial magnetic heterostructures.

Effects of electrode material and configuration on the characteristics of planar resistive switching devices

We report that electrode engineering, particularly tailoring the metal work function, measurement configuration and geometric shape, has significant effects on the bipolar resistive switching (RS) in lateral memory devices based on self-doped SrTiO3 (STO) single crystals. Metals with different work functions (Ti and Pt) and their combinations are used to control the junction transport (either ohmic or Schottky-like). We find that the electric bias is effective in manipulating the concentration of oxygen vacancies at the metal/STO interface, influencing the RS characteristics. Furthermore, we show that the geometric shapes of electrodes (e.g., rectangular, circular, or triangular) affect the electric field distribution at the metal/oxide interface, thus plays an important role in RS. These systematic results suggest that electrode engineering should be deemed as a powerful approach toward controlling and improving the characteristics of RS memories.

Asymmetric electroresistance of cluster glass state in manganites

We report the electrostatic modulation of transport in strained Pr0.65(Ca0.75Sr0.25)0.35MnO3 thin films grown on SrTiO3 by gating with ionic liquid in electric double layer transistors (EDLT). In such manganite films with strong phase separation, a cluster glass magnetic state emerges at low temperatures with a spin freezing temperature of about 99 K, which is accompanied by the reentrant insulating state with high resistance below 30 K. In the EDLT, we observe bipolar and asymmetric modulation of the channel resistance, as well as an enhanced electroresistance up to 200% at positive gate bias. Our results provide insights on the carrier-density-dependent correlated electron physics of cluster glass systems.